Dihydroxyalkyl alkenylaryl ethers and polymers therefrom



DIHYDRGXYALKYL ALKENYLARYL E'I'HERS AYE) PQLYWIERS THEREFROM Gaetano F. DAlelio, Pittsburgh, Pa., assignor to Koppers Company, Inc., a corporation of Delaware N Drawing. Application October 20, 1954 Serial No. 463,612

30 Claims. (Cl. 260-47) This invention is concerned with certain new dihydroxyalkyl alizenaryl ethers. It is concerned with these substances in a monomeric as Well as polymeric form. Furthermore, the invention is concerned with insoluble or cured polymers which can be obtained by treating dihydroxyalhyl alkenaryl ether polymers to cause crosslinking.

The invention is particularly concerned with dihydroxyalkyl alkenaryl ethers of the formula in which Ar is an arylene radical, R is chosen from the class consisting of hydrogen and methyl, and n is an integer having a value no greater than 8.

In particular the invention is concerned with dihydroxya lyl vinyland isopropenylaryl ethers. It will be realized that polymers of the monomers of this invention contain dihydroxyalkyl groups. These polymers are useful in many polymer applications such as for molding, coatings, laminating and adhesives by, for example, esterification with drying oil fatty acids for paints, reaction with polyisocyanaes or polyoxiranes and the like.

As used herein the term polymer embraces both homopolymers and copolymers. The term copolymers as used herein embraces polymeric materials derived from the polymerization of two or more monomeric materials. That is, 2,3,4,5 ad infinitum copolymerizable monomeric substances can be copolymerized to produce a copolytner. As used herein the terms parts and percentages indicate parts and percentages by weight unless otherwise specified. The invention is illustratedby,

but not restricted to, the following preferred embodiments:

EXAMPLE I J Z-vz'nylplzenoxy -2,3-propmzedi0l One hundred parts of 1-(2-vinylphenoxy)-2,3-epoxypropane, obtained from 2-vinyl phenol and epichlorohydrin by the procedure described in Example f my copending application, Serial No. 463,608, filed concurrently herewith, is boiled in dilute aqueous caustic for one hour. The mixture is cooled and acidified with hydrochloric acid. volume portions of ether, the portions combined, and the ether removed by evaporation. The compound is recrystallized from benzene. There is obtained a white solid melting at 9192 C. which is characterized by analyses for carbon and hydrogen which are in substantial agreement with the theoretical values, by analytical hydrogenation which indicates 1.1 double bonds and by the paranitrobenzoate derivative of the hydrogenated product which has a melting point of 125-126" C.

epoxypropane, obtained from 4-isopropenyl phenol and epichlorohydrin by the procedure described in Example The mixture is extracted with five equal.

States atent O M Patented Sept. 2, 1958 II of my copending application, Serial No. 463,608, filed concurrently herewith, is treated according to the procedure of Example I above. There is obtained the desired product which, upon crystallizations from benzene, yields white plates melting at 111.5 C. The product is characterized by carbon and hydrogen analyses which are in substantial agreement with the theoretical values, by analytical hydrogenation which shows 1.05 double bonds, and by the bis-paranitrobenzoate derivative of the hydrogenated product which melts at 96-96.5 C.

EXAMPLE III 1 3 -vinyl phenoxy -2,3-pr0panedi0l 1--(3-vinylphenoxy)-2,3-epoxypropane, obtained from 3-vinyl phenol and epichlorohydrin by the process described in my copending application, Serial No. 463,608, filed concurrently herewith, is treated according to the procedure of Example I. There is obtained the desired compound which is characterized by carbon and hydrogen analysis and by anaiytical hydrogenation which give values in substantial agreement with the theoretical values.

EXAMPLE IV 1 (2-vinylphen0xy -3,4-b uzanediol 1-(2-vinylphenoxy)-3,4-epoxybutane, obtained from 2- vinyl phenol and 1-chloro-3,4-epoxybutane by the pro cedure described in my presently copending application, Serial No. 463,608, filed concurrently herewith, is treated according to the procedure of Example I. There is obtained the desired compound which is characterized by carbon and hydrogen analyses and by analytical hydrogenation which give values in substantial agreement with the theoretical values.

EXAMPLE V 1 -(4-isopr0penylphenoxy -3,4-butanediol One hundred parts 1-(4-isopropenylphenoxy)-3,4- epoxybutane, obtained from 4-isopropeny1 phenol and 1-chloro-3,4-epoxybutane by the procedure described in my presently copending application, Serial No. 463,608, filed concurrently herewith, is treated according to the procedure of Example I. There is obtained the desired compound which is characterized by carbon and hydrogen analyses and by analytical hydrogenation which give values in substantial agreement with the theoretical values.

It will be realized that the various dihydroxyalkyl alkenylaryl ethers of this invention can be obtained by the hydrolysis of the corresponding epoxyalkyl alkenylaryl ethers described in my above-mentioned application. Additionally, it is to be noted that the dihydroxy compounds of this invention are produced in minor quantities in the preparation of the corresponding epoxyalkyl alkenylaryl ethers by the reaction of an alkenylaryloxy salt with an epihalohydrin as described in my above-mentioned application. These dihydroxy compounds are characterized by analyses for carbon and hydrogen and analytical hydrogenation.

EXAMPLE VI One hundred parts 1-(2-vinylphenoxy)-2,3-propanediol obtained as in Example I are admixed with one-half part 'benzoyl peroxide. The atmosphere is alternately purged with nitrogen and evacuated to approximately 0.5 mm. mercury. The compound is then heated at 105 C. for approximately 2 days. There is obtained polymeric l-(2-vinyl)-2,3-propanediol, which is a linear, soluble polymer.

Similarly, linear, soluble polymers of 1-(3-viny1- phenoxy) -2,3-propanediol (obtained as in Example 111), 1-(2-viny1phenoxy)-3,4-butanediol (obtained as in Example IV) and of the other dihydroxyalkyl alkenylaryl ethers ofi this invention are obtained by following the foregoing-procedure. For-the benzoylperoxideutilizedthere in, there can be substituted a1 variety of peroxy catalysts such as hydrogen, acetyl, acetyl benzoyl phthalyl and. lauroyl'peroxides, tertiary-butyl hydroperoxides, etc., and other percompounds, for example, ammoniumtpersulf'ate', sodium-persulfjate, sodiumperchlorate and the like.

EXAMPLE VII Onehundred parts 1 -(4-isopropenylphenoxyylfi propanediol is-polymerized according to the procedure-of ExampleVI. There is obtained linear, soluble polymeric: 1 ('4-isopropenylphenoxy) -2,3-prop anediol.

Similarly, the various dihydroxyallgyl isopropenylaryl" ethers of this invention, forexample, 1-(4-isopropenylphenXy)-3,4-butanediol, (obtained as in Example V), can be polymerized according to the procedure of Example V- to,yiel d linear, soluble .homopolymers.

EXAMPLEVIII Ninety parts styrene lt) parts 1-(2-viny1phenoxy):-2,3+ propanediol and one-halfpart benzoyl peroxide areaad; mixed-inia reaction vessel and the atmosphere swept out and filled withnitrogen. The polymerizable mass is. heated at 80;1055 G tor, approximately Zdays. Thereis obtained a soluble, linear cop olymer.

EXAMPLE IX Example VIII. is repeated substituting for, the. vinylphenoxy, diol. there utilized an equalweight of 1 -(4-iso-v propenylphenoxy)-2,3-propanediol (obtained as in, Ex? ample II); There is obtained a light yellow, linear, S0111? ble copolymer.

EXAMPLE X,

EXAMPLE XII Example VIII'i s repeated substituting for the. styrene.

there used, an equal Weight ofacrylonitrile tained a linear, soluble copolymer.

. EXAMPLE XIII There is ob- Example IXisrepeatedutilizing in place of the styrene,

there-utilized; an equal weight of acrylonitrile. There is.

obtained a linear, soluble copolymer.

EXAMPLE-XIV Example VIII is repeated substituting for the styrene there utilized, an equal weight of butadiene. There is'ob; tained a linear, solublecopolymer.

EXAMPLE XV Example IX is repeated substituting for the styrene there-used, an equalweightofbutadiene; There-is ob tained, alinear; soluble copolymer;

EXAMPLE XVI Example. VIII is repeated," substituting riot-the styrene I there-utilized, anequal weight of methyl methacrylate;

There;;is obtained a linear,,soluble copolymer.

. 7 EXAMPLE XVII Example IX is, repeated substituting for, the." styrene,

, there. utilized, an equal, weightrofrrnethyl vmethacrylater- There is obtaineda linear, solublecopolymer,

Examples VllI-XVII inclusive illustrate the preparation ofcopolymers of the various compounds of this invention and copolymerizable: ethylenic monomers.

It is to be realized that any of thevarious dihydroxyalkyl alkenylaryl ethers of this invention can be substituted for the particular compound ,of the invention utilized in the immediately foregoing illustrations of copolymerizati'om to; yieldicopolymers. Furthermore, there can be utilized mixtures of two or more: of the compounds of this invention in the preparation of copolymerseither of the compoundsof'thi'sinventionaloneor in combination with a copolymerizable ethylenically unsaturated monomer, or mixtures- 0f two or" more such copolymerizable ethylenically unsaturatedmonomers.

As noted aboveein connection withthev homopolymerization of the compounds of this invention various per compounds can be used as catalysts in preparation of the above-described copolymers.

XVIIL One hundred; parts of the polymer of Example VI are admixed? with 4' parts 2,4-toluenediisocyanate and the mixture heatedfor one hour at C. Thereis obtained. an' insoluble, infusible, cross-linked polymer;

There can be substituted forthe. polymer of Example VI- anyofthe' various polymers of'the compounds of this invention such as, for example'flhe polymers of Examples VII through-XVII inclusive. There areiobtained insoluble, iniusible, cross-linked copolymers. Additionally, there can be substitutedlfor the.2,4-toluene diisocyanate,

other dii'socyanates suchas phenylenediisocyanate, 2,6--'

toluenediisocyanate, 1,5 naphthalenediisocyanate, chloro-l:ph'enylenee2,4-diisoeyanate, 4,4 xenylenediisocyanate,.. methylene. bis.,-(4-phenylisocyanate), hexamethylenediisocyanate, tetramethylenediisocyanate and theliket The amount of. these;diisocyanates utilized is.

Example XIX is repeated utilizing in place of the diglycidylietherof bisphenol' an equal weight of the resin descriheti at column 7-of my U. S. Patent 2,658,885, grantedzNov: 10'; 1953. There is obtained a thermoset resin. It will be realized that the various epoxyalkoxy.

hydrocarbon-substituted phenol aldehyde resins described in that patentcan beutilizedin the foregoing procedure. Additionally the epoxyalkoxy chlorine-substituted-phencl aldehyderesins described in my U. 3. Patent 2,658,884,

grantedNov. 10, 1953, can b'e'utilized in the foregoing procedure.

It is t'o -be =n0tedthat inplacej of ethylene diamine catalyst-utilized in Example XIX there can be substituted equivalent portionsofsuch amine catalysts as tetrahydroquinoline and' piperidine to obtain; substantially similar results.

EXAMPLE XXI One; hundredparts 'of' the polymer *of 1 Example VHIl is heated,.with- -parts of-linseed-ifatty acids ina closed stainless-steel?kettleequipped; with'an agitator, a means for, introducing; anuinert gas-below the surface of the liqnidcontentssand a gasolltlet means. Themixture is heated to, approximately-175. C. and: agitated while nitrogen is passed through the reaction mass to carry oft" the water produced by the esterification reaction.

There is obtained-a modified polymer having greater oilsolubilitythan-theoriginalpolymer,- said modified poly:

merhbeing particularly :useful in. theipreparation of. paints and.varnishes-.:- It Willrbfl realizedithat'forthe-linseed.fatty acids utilized above, there can be substituted a variety of drying oil and semi-drying oil fatty acid compositions. Such fatty acids are those derived from linseed, dehydrated castor, tung, perilla, soybean, oiticia, fish, hempseed, poppy seed, sunflower oils, etc. Further, the various linear, soluble polymers and copolymers of the monomers of this invention can be esterified according to the foregoing procedure to yield products of increased oil solubility and of utility in the preparation of paints and varnishes.

In those instances in which the hydroxyalkyl alkenylaryl ethers are copolymerized with ethylenically unsaturated monomers which do not possess other potentially reactive groups it is desirable that at least one percent of the 'dihydroxyalkyl alkenaryl ethers be included in the polymer molecule for cross-linking purposes such as, for example, by reaction with polyisocyanate or polyoxirane compounds as heretofore described.

It will be realized that the dihydroxy compounds, of this invention, upon esterification, yield products possessing greater oil solubility than do the esterified monhydroxy compounds, as a result of which they possess a wider range of utility in the preparation of paints, varnishes, and the like.

t will be realized that the hydrophilic properties of the monomers and polymers of this invention can be increased by reaction by the introduction of a plurality of hydroxyalkylene groups into the molecule such as, for example, by the reaction of an alkylene oxide such as ethylene or propylene oxide with a hydroxyl group of the monomers or polymers of this invention. In particular, the epoxyalkyl alkenylaryl ethers described and claimed in my copending application filed concurrently herewith, can be reacted with the monomers and polymers of this invention to produce desirable modifications thereof.

While the invention has been described with reference to particular embodiments thereof, it will be understood that in its broadest aspects the invention may be variously embodied within the scope of the invention as set forth herein and in the appended claims.

What is claimed is:

1. A dihydroxyalkyl alkenylaryl ether of the formula in which Ar is an arylene radical, R is chosen from the class consisting of hydrogen and methyl, n is an integer having a value of at least 3 and no greater than 8 and in which the hydroxyl groups are substituted on adjacent carbon atoms.

1-( 4-vinylphenoxy)-2,3-propanediol. 1-(2-vinylphenoxy)-2,3-propanediol. l-(4-isopropenylphenoxy)-2,3-propanediol. 1-(3-isopropenylphenoxy)-2,3-propanediol. 1- 3-vinylphenoxy) -2,3-propanediol. A homopolymer of a dihydroxyalkyl alkenylaryl ether of claim 1.

8. A polymer of a dihydroxyalkyl alkenylaryl ether having a plurality of repeating units of the formula izable ethylenically unsaturated monomer comprises butadiene.

13. A copolymer of claim 9 in which the copolymerizable ethylenically unsaturated monomer comprises acrylonitrile.

14. A copolymer of claim 9 in which the copolymerizable ethylenically unsaturated monomer comprises maleic anhydride.

15. A copolymer of claim 9 in which the copolymerizable ethylenically unsaturated monomer comprises methyl methacrylate.

16. An insoluble polymer of a dihydroxyalkyl alkenylaryl ether of claim 2 and, at least one other polymerizable ethylenic monomer, said polymer containing a plurality of cross-linkages derived from hydroXy groups of said dihydroxyalkyl groups.

17. An insoluble polymer comprising 1(2-vinylphenoXy)-2,3-propanediol and at least one other polymerizable ethylenic monomer, said polymer containing a plurality of cross-linkages derived from hydroxy groups of said dihydroxyalkyl groups.

'18. An insoluble polymer of claim 16 in which the copolymerizable ethyleneic monomer comprises styrene.

19. An insoluble polymer of claim 16 in which the copolymerizable ethylenic monomer comprises butadiene.

20. An insoluble polymer of claim 16 in which the copolymerizable ethylenic monomer comprises acrylonitrile.

21. An insoluble polymer of claim 16 in which the copolymerizable ethylenic monomer comprises maleic anhydride.

22. An insoluble polymer of claim 16 in which the copolymerizable ethylenic monomer comprises methyl methacrylate.

23. A copolymer of 1-(4-vinylphenoxy)-2,3-oropanediol and at least one other copolymerizable ethylenically unsaturated monomer.

24. A copolymer of 1-(4-isopropenylphenoxy)-2,3- propanediol and at least one other copolymerizable ethylenically unsaturated monomer.

25. A copolymer of 1-(3-isopropenylphenoxy)-2,3- propanediol and at least one other copolymerizable ethylenically unsaturated monomer.

26. A copolymer of 1-(3-vinylphenoxy)-2,3-propanediol and at least one other copolymerizable ethylenic unsaturated monomer.

27. An insoluble polymer comprising 1-(4-vinylphenoxy) -2,3-propanediol and at least one other polymerizable ethylenic monomer, said polymer containing a plurality of cross-linkages derived from hydroxy groups of said dihydroxalkyl groups.

28. An insoluble polymer comprising 1-(4-isopropenylphenoxy)-2,3-propanediol and at least one other polymerizable ethylenic monomer, said polymer containing a plurality of cross-linkages derived from hydroxy groups of said dihydroxyalkyl groups.

29. An insoluble polymer comprising 1-(3-isopropenylphenoxy) 2,3-propanediol and at least one other polymerizable ethylenic monomer, said polymer containing a plurality of cross-linkages derived from hydroxy groups of said dihydroxyalkyl groups.

30. An insoluble polymer comprising 1-(3-vinylphenoxy) -2,3-propanediol and at least one other polymerizable ethylenic monomer, said polymer containing a plurality of cross-linkages derived from hydroxy groups of said dihydroxyalkyl groups.

References Cited in the file of this patent UNITED STATES PATENTS 599,123 Endemann Feb. 15, 1898 FOREIGN PATENTS 625,493 Great Britain June 29, 1949 651,334- Great Britain Mar. 14, 1951 

1. A DIHYDROXYALKYL ALKENYLARYL ETHER OF THE FORMULA 